Electrolysis of liquids.



y and resident of Pelikangass SAS PATENT F ion.N

JEAN BILLITER, VENNA, USTRA-HUNGARY.

vEneducation of 'Letters Fatent. application filed muy e, i910. sriaino. 571,003.

Patented Sept. 3, 19112.

-To all wit/)rgb it may concern.'

Be it 'known that LJEANBILLITER, a subject ofthe Emperor of, AustriaHungary, 1G, Vienna, Austria-Hungary, have invented a cer in new and userul Improvement in the Elev troly'sis of Liquids, of which the.tolli-wiA is a specification;

-led to these improvements were either a rational decomposition and circulation, or

'gradually diminished.

the quick removal of the prrxluctsA from the cathode out of they range of the current. The methods, Worlrinff on these principles, possess, besides their ohvious advantages,'the common disadvantage, that the space for the anode is entirely vshut mi' by avdiaphrag'm, through which the feed-solution is brought into the space for the cathode. F or au undisturbed worlring; the speed of the flow' must therefore be carefully regulated; and, from time to time adjusted', as the di.phragrnsA property of lettinggthe solution through is The diaphragme need cleaning and repairing; at fixed intervals, and the baths have therefore to he opened; and the Whole arrangement requires a strict and careful Watching. ln this respect-the electrolysis Withcuitdiaphragm, alte-l the Well Known f'ussig bell-method is much simpler.l ln that case there is no diaphragm, Whose" 4roperly of permitting the solution to passthrongh changes,and 'requent, cleaning and openiir'g of thehaths is therefore unnecessary, andtheworking may be continued thronghoutthe year, Against these 'adirantages the method has,l1o`weve1', severa' serious" disadvantaged via.; the strength of thecurrent isvery small, und the recess is in' consequence very tedious and difiicult to follow. The dividing of the eed-solution, etc., into the numerous small cells is more` complicated, et'c. .flhe necessary concentration of' the lye is smaller, as 1s also the current exchange.

The inventor lies endeavored to devise and.

work out a method that combines the adventages' of both systems, without possessing their disadvantages; also a method in '[Which 'the anode and the cathode spaces are not separated by continuous diaphragme, and which does not require a frequent c0nsidf eration of thei'diaphragme* condition g* but which, nevertheless, permits an operation with very stronol currents and 'ood cnrrent. b l1 exchange; .The production of stronger currents 'is worth aiming at, not only in order to increase the etliciency of the electrolysis as well as the gain for the production oiE smaller space ivith cheaper apparatus; lout4 also to bring about better currenty exchange und higher concentration in all processes in ich a separation of the products is donc decomposition or chemistry since the dilv and mixing of the layers naturally o much easier, the longer the conollo l tact or the layers 1s lasting; and because the' keeping anode will tollow easier on account of the increased speed ot the flow' producing away or the alkali layer from the stronger current. For this reason inventors such as nardson, Johanne and WV. Bein, have for seine time been trying` to increase the curr strengthl in the bell method. ltichardson :nid Johanns (in British Paty ent 569e i893- and U. S'. Patent 724,580); in with this object in View,

cathode-bars hf ore the opening of the bell,

providing the "e with gutters, open at both ends, in ci to remove the cathode water, While preserving the decomposition as far as possible. Later on XV. Bein (Geiny man Patent 107,917) proposed in yla quite different construction, where, in place of impenetrable screens, such as an osiiiotic membrane' kind of porous diaphragm) `is used, which permit-s the current to ypass. riie'circulation should follow in a similar' manner in accordance with Richardson and Johanne as in the hell-method; while Be` allows the solution to pass the cathode ina side movement. l'. ain not aware of these proposalsv having come to any practical um. l'supposeithat they did not iull the expec-l tations.. Agt zleast., l have not been able to obtain any-results in my experimental tests of these methods. in order to provethe Wrong principles, l undertook further experiinents and arrived at the following con?" clnsions:

4l. lin methods heretofore in use, the ano-,P ly.te,during the circulation,4 'passes almost--v los Aentirely by the edges of appear under the coverin the outer vessel, crawls so to speak, under the lower edge of the bell, and leaves the middle and lower layers altogether untouched. Such circulam can therefore not be rational, since the fluid currents and the distribution of currents do not correspond; since furthermore the alkali is not prevented from reaching the anode when removed from the wall of the bell. As the roof shaped gutters are open at both ends, the water bi'lbbles that will produce a movement of the duid in t e cells distributing the decomposition.

2. A. side movement does not permit of a vcomplete separation of the layers, since this side movement, as shown in paragraph 1, will cause friction' between the separating layers, which is apt t producemixing instead.

3. The -ten'sion in the'bath will rise to an abnormal height, almost to breaking point in the current, if sundry means were not applied toconstantly remove the water.

' The remedies were not far to find after the above had been proved. The'ielectrolyte must, during its circulation, be conducted orosswise to the surface of the cathodes and simultaneously over the whole surface; the

revented from causing changes in the fluid surface (waves or 'ripples) which will frustrate the decomposition; producing harmful curfents or curtailing the course of the currents. A conitratesone form of cathode.

ist-ruction to fulfilthese requirements is shown in longitudinal section in Figure 1 and in cross section in Fig. 2. Fig. 3 illus- Fig. 4 illustrates this form in groups, and Fig. 5 illustrates another modification. 1

A reservoir or vessell made of cement, reinforced concrete or stone is provided -with a bell or cover Q of similar material.

The bell is somewhat shorter than the vessel 'and leaves a chamber 15 at one end of the bath. In the bottom of the vessel lis an opening 3 continued by a channel 4, terminating with a vertical pipe 5 having an outlet tube 6. The' bell 2 receives the anode 7 connected through 8 `to the positive pole. The bell is only partially separated from the grate-shaped cathode 10 with its covering 12. 'Ihe manner of inserting and connecting the cathode is evident from the figures. rl`he feed-solution is introduced at 13, the chlorin gas is liberated through pipe 9 and the product from the cathode' at 6. This arrangement permits of lthe steady conducting of the salt solution vertically down to the cathode surface. YIn order to get thccirculation to correspond still better' with the current distribution it is advisable lo fill the spaces between the staves or bars of the cathode-grate with impenetrable strips 1T (made for instance of glass) which 'ing at the opposite are arranged higher'or lower according to the cathode stirface. The cathode -bars should be made las narrow as possible and not placed too farfapart.

The cathodes I0 are made of cast iron, wrought iron, iron wire or wire netting and they reach under one edge of the bell length- Wise of the bath almost horizontally, restside with the ends on a ledge of the vessel. The vertical part thereof leads up through the side chamber 15 to the conductor 11. built as indicated, said cathodes consisting of iron staves 10 covered by a conductive or non-conductive membrane or sheath 10* and inclosed by a covering 12 of asbestos paper, asbestos cloth, or cement, which provide means for leading ofi the water, At their lower ends (to the left of Fig.V 1) these gutters 'are closed for the reason given, viz., for preventing fluid movement along the cathode. Close under the edge of the bell they haveI 'aielbow shaped bend and are led into pipes ofI the same material or of sheet metal, which`c`onduct the gas upward. The horizontal parts have an inclination of from 2 to 4', This arrangement worked satisfactorily, but seemed still to.

require some improvement, because of the small ripples on the surface caused by the The cathodes should be constant appearance of bubbles from the'.

water constituents, which still made a steady. decomposition somewhat diiiicult,

particularly as the electrode covering might itself be set in motion. Increased injurious tension might, besides, voften appear, when the water constituents inflate the membrane,

forming deformed, injurious spaces. To remove these inconveniences, I inclose the cathodes on all sides in a conductive membrane 10a (cement for instance) or by any other rigid construction with the same object' of totally preventing a deformation caused by the water constituents. For this purpose I have used electrodes indicatedlin Fig. 4: for rigid membrane (such as asbestos cardboard with a coating of cement) where I arrange several cathode staves in a still' pipe. These electrodes kept, indeed, very well in use, the loss in tgnsion was, however', not altogether overcoliie. In order to' improve on the same, I have designed the device shown in Fig'. 5,"usi ng flexible alkali containing materials *very thin and conductive as membrane, such for instance, as asbestos paper, asbestos cloth or similarly preparedmaterials. .These membranes by meansof a spring wire 14, (see Fig.' 2)

.or in any other similar manner, over the cathode. As another instancethe horizontal part of the cathode might be made-of wire netting bent slightly 'convex on top,

with enough spacing to 1t so that the mein-Jia or pouchesclosed at the lower end but open Leanser; y

brane d rawn over it without' anyjllother means, 1s held suspended. "Wlth this ar` rangement, 'the membranes form long bags at the upper end, allowing the gases to escape at 16. All changes in volume and all ripples in the fluid caused by the water con- "stituentsl will be kept inside the bag and f will not be transmitted` outside to the prin- *open endsvof the'bag may reach up to a litchamber 15, but it is better, however, if itl extends to the-,level or a little above.

cipal ycontingents of .the electrolyte. The

tle below the level of the fluid in the side e The Vertical part of the pouch or bag in the side l `chamber need not be expanded, when this chamber 1s not connected by larger openings with the inner one. The use of elastic electrodesor of weights serves the double purpose of preventing a change in volume or form of the membrane and to press the cathode metal 10 hard against the membrane, 1n order to prevent a collection of `water -ingredients between them, and the consequent increase'of tension or breaks in the current. The materials, asbestos paper or asbestos cloth, preferably used for the pouch or bag are even in the expanded con dition quite gas tight, when soaked in the fluid and when below the level thereof.

In the abovedescribed arrangements the eatholyte remains, without beingliniluenccd by the electrolyte flowing away, all the time in the immediate neighborhood ofthe cathode; the electrolysis operating in the following manner: In closing the current,

trolyte in the immediate neighborhood of.

-the cathode. The OH. ions then appear on the inside of-the men'ibranc,respectively'on the edge of the gutter. On account of the narrowness of the paths lof the current, the

decrease in tension in the membrane at the,V p

lower edges of the gutter is greater than in other parts of the electrolyte. The OH ions will therefore quickly travel, influenced by the higher potency at .these places, toward the anode, and the alkali will form a specifically heavy layer close above the cathode. The fall in tension is smaller outside the membrane and may be brought to zero by opposing currents (by introducing the feed solution above the cathode surface), so that the alkali containing, heavy layer in a short while will fill the lower part of thebath a' little above the cathode, while the anolyte will deposit itself in a specifically lighter layer on top thereof. In opposition to all heretoforeknown arrangements the alkali is diffused (principally by electric transmission) from the cathode chamber proper through the membrane, and is carried away outside the cathode chamber by the outward How of the electrolyte. The catholyte consisting of concentrated alkali, the loss in tension at the cathode and at the membrane will be very small. The cathode product ofthe electrolysis will therefore appear outside the cathode chamber inthe solution coming from the anode and holding some free chlorid, without againpassing by the cathode, as formerly. Traces of hypochlo'- rite are found, which are not, a's'heretofo're, part-ly removed by cathode reduction during reproduction of chlorin, but are discharged together with the product at 6. Although these traces are almost of no consequence; if it sho-nld be so desired, they mayeasily be removed by any of the many chemical ways. They might also easily be removed electrolytically, by introducing a secondary cathode, by which the product from the electrolysis is permit-ted to pass immediately before leaving the bath at 6,' and by sending about l (.70 of the current through the secondary cathode; The pipe 5 might for instance be made of iron and connected with the negative pole, or ,an iron rod may bc inserted into the pipe to serve as cathode, etc.

The principal advantage of this method, just described, over the bell-method, consists therein, that l have succeeded to prolduce muchhigher current strength with exchange and concentration have already been demonstrate-d in the beginning. lVhile a current of not more than 200 amperes per s( uare meter may be obtained with a tension ofB-z'- to et volts in the bell-method; the same voltage will produce 50() amperes in the present method. By heating the solution in thebath the comparison 'willbe still more favorable.

These cells whose action in salt electrolysis has been described are equally useful in the electrolysis'of potassium chlorid.

llhat is claimed isz.

1. An ap aratus for electrolyzing liquids having catodes arranged in` horizontal strips; conduits carrying away gas and ar-.

ranged to cover said cathodeS, and'said conduits being/closed to prevent the free circula-tion of electrolyte.

,ein apparatus for electrolyzing liquids lm ving cathodes arranged in horizontal strips; conduits carrying away gas and perme'able to current, said conduits being provided with membranes complet ely surrounding the cathode, whereby the Acathode product escapes only by filtration.

An. apparatus for electrolyzing liquids having cathodes arranged iu horizontal strips, conduits covering'said cathodes and comprising a membrane permeable to current stretched over the electrodes, and av suitably arranged auxiliary means adapted to prev-ent the formation of gas spaces.

4. An apparatus for electrolyzing liquids hai-'ing cathodes arranged in horizontal strips; tubular conduits covering said cathodes `and adapted to carry away gas and cathode through which the electrolyte mayA be discharged.

5. An apparatus alkali solutions comprising a vessel, an

anode, a cathode disposed horizontally ofthe vessel, a Jfabric casing for the cathode pro- -viding a gas discharging means, said fabric permitting of passage of the current therethrough, and having means to preventmovcment along the cathode of the flowing electrolyte, for the purpose specified.

6. An apparatus' for the electrolysis of alkali solutions comprising aI `vessel, an

" anode, a cathode formed of a plurality of horizontally disposed'vyand spaced members providing a grate, said grate providing' an anode and a cathode chamber, non-conductive strips y'for covering the spaces between i said cathode members, but permitting of the passage therethrough of the electrolyte whereby to obtain uniformity in the circulation of the fluid and current; andan outfor the electrolysis ofr :let in the vessel below the cathode, for the purpose specified.

7. An apparatus for the electrolysis of alkaliA solutions comprising a vessel, an anode, a cathode inclosed by a membrane substance, a current conductivemembrane inclosing the cathode membrane and having means for holding the same thereon'to'prevent injurious changes of form and injurious gas spaces; and an outlet in the vessel below the cathode, for the vpurpose specified.

8. An apparatus for the llelectrolysis' of alkali solutions coinprisingi a vessel, an anode, a cathode inclosed by .a plurality of horizontally disposed membrane substances providing a grate, said grate providing'an anode and acatliode chamber, and the spaces between the cathode elements permitti/ of passage therethrough of the electro yte whereby to obtain uniformity in the circu lation of he fluid and current, each of said cathode membranes being inclosed by a current conductive membrane sheath, means for holding the respective cathode membranes on their cathodes whereby to prevent injuri- -ous lchanges of form or injurious gas spaces; A

and an outlet in the vessel below the cathode for the purpose specified.

In testimony whereot I aflix my signature in presence 'of two witnesses.

' JEAN BILLITER.

Witnesses AUGUST FUGGER, -RoBERT W, HainGAirriaaRF 

